Bimolecular reactions on sticky and slippery clusters: Electron-induced reactions of hydrogen peroxide

Nanoparticles can serve as an efficient reaction environment for bimolecular reactions as the reactants concentrate either inside the nanoparticle or on the surface of the nanoparticle. The reaction rate is then controlled by the rate of formation of the reaction pairs. We demonstrate this concept on the example of electron-induced reactions in hydrogen peroxide. We consider two types of nanoparticle environments: solid argon particles, only weakly interacting with the hydrogen peroxide reactant, and ice particles with a much stronger interaction. The formation of hydrogen peroxide dimers is investigated via classical molecular dynamics (MD) simulations on a microsecond timescale. With a modified force field for hydrogen peroxide, we found out a fast formation and stabilization of the hydrogen peroxide dimer for argon nanoparticles, while the reaction pair was formed reversibly at a much slower rate on the water nanoparticles. We have further investigated the electron-induced reactions using non-adiabatic ab initio MD simulations, identifying the possible reaction products upon the ionization or electron attachment. The major reaction path in all cases corresponded to a proton transfer. The computational findings are supported by mass spectrometry experiments, where large Ar-M and (H2O)(M) nanoparticles are generated, and several hydrogen peroxide molecules are embedded on these nanoparticles in a pickup process. Subsequently, the nanoparticles are ionized either positively by 70 eV electrons or negatively by electron attachment at electron energies below 5 eV. The recorded mass spectra demonstrate the efficient coagulation of H2O2 on Ar-M, while it is quite limited on (H2O)(M).

Automated summary

Nanoparticles can provide efficient reaction environments for bimolecular reactions by controlling the formation rate of reaction pairs. In this study, we investigated electron-induced reactions in hydrogen peroxide in two types of nanoparticle environments and found that the reaction rate was faster in argon nanoparticles than in water nanoparticles. Computational simulations and mass spectrometry experiments were used to identify the reaction products and confirm the findings.